Substituted methyl isopropyl cyclohexenones, organoleptic uses thereof and process for preparing same

ABSTRACT

Described is the genus of compounds defined according to the structure: ##STR1## wherein one of the dashed lines represents a carbon-carbon double bond and the other of the dashed lines represents a carbon-carbon single bond; wherein R 4  represents methyl or ethyl; wherein one of R 1 , R 2  and R 3  represents 2-methyl-1-propenyl or 2-methyl-1-propylidenyl; and the other of R 1 , R 2  and R 3  represent hydrogen; with the provisos that: 
     (i) when the dashed line at the 3-4 position is a double bond, then R 3  is hydrogen or 2-methyl-1-propenyl; 
     (ii) when the dashed line at the 2-3 position is a double bond, then R 2  is hydrogen or 2-methyl-1-propenyl; 
     (iii) when R 4  is ethyl, then R 2  is methyl and the double bond is at the 2-3 position; and 
     (iv) when R 4  is methyl, then R 2  is hydrogen; 2-methyl-1-propenyl or 2-methyl-1-propylidenyl; 
     with the members of said genus being novel compounds when R 4  is ethyl or when R 4  is methyl and the double bond is at the 3-4 position or when R 4  is methyl and the double bond is at the 2-3 position with R 3  being hydrogen, which compounds are useful in augmenting or enhancing the aroma or taste of consumable materials including smoking tobacco compositions, smoking tobacco articles, perfume compositions, colognes and perfumed articles (e.g. solid or liquid anionic, cationic, nonionic or zwitterionic detergents, cosmetic powder compositions, fabric softener compositions and fabric softener articles). Also described is the process for preparing the compound.

This is a divisional of application Ser. No. 343,580, filed 1/28/82 nowU.S. Pat. No. 4,400,311.

BACKGROUND OF THE INVENTION

The instant invention provides substituted 3-alkyl-5-isopropylcyclohexenones a number of which are novel, defined according to thestructure: ##STR2## wherein one of the dashed lines represents acarbon-carbon double bond and the other of the dashed lines represents acarbon-carbon single bond; wherein R₄ represents methyl or ethyl;wherein one of R₁, R₂ or R₃ represents 2-methyl-1-propenyl or2-methyl-1-propylidenyl and other of R₁, R₂ and R₃ represents hydrogen;with the provisos that:

(i) when the dashed line at the 3-4 position is a double bond, R₃ ishydrogen or 2-methyl-1-propenyl;

(ii) when the dashed line at the 2-3 position is a double bond, R₂ ishydrogen, methyl or 2-methyl-1-propenyl;

(iii) when R₄ is ethyl, then R₂ is methyl and the double bond is at the2-3 position; and

(iv) when R₄ is methyl, then R₂ is hydrogen; 2-methyl-1-propenyl or2-methyl-1-propylidenyl;

with the members of said genus being novel compounds when R₄ is ethyl orwhen R₄ is methyl and the double bond is at the 3-4 position or when R₄is methyl and the double bond is at the 2-3 position with R₃ beinghydrogen.

Chemical compounds which can provide peppery, sweaty, guiacwood-like,green, burnt grass, vetiver-like, sandalwood-like, fresh, floral,citrusy and spicy aroma nuances with sauge sclaree topnotes and muskyundertones are highly desirable in the art of perfumery. Many of thenatural materials which provide such fragrances and contribute suchdesired nuances to perfumery compositions are high in cost, unobtainableat times, vary in quality from one batch to another and/or are generallysubject to the usual variations of natural products.

By the same token, materials which can provide woody, peppery andcitrusy aroma and taste nuances in smoking tobacco compositions andsmoking tobacco article components prior to smoking and can impart asweet, citrusy character to smoke flavor in smoking tobacco compositionsand smoking tobacco articles on smoking are highly desirable in the artof smoking tobacco flavoring. Many of the natural materials whichprovide such aroma and taste nuances are high in cost, unobtainable attimes, vary in quality from one batch to another and/or are generallysubject to the usual variations of natural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance, or augment the essential flavor andfragrance notes provided by natural essential oils or compositionsthereof.

The fundamental problem in creating artificial flavor and fragranceagents is that the artificial flavor or fragrance to be achieved be asnatural as possible. This generally proves to be a difficult task sincethe mechanism for flavor and/or fragrance development in many fragrancematerials and tobacco products is not completely known. This isnoticeable in products in the fragrance area having peppery, sweaty,guiacwood-like, green, burnt grass, vetiver-like, sandalwood-like,fresh, floral, citrusy and spicy aroma nuances with sauge sclareetopnotes and musky undertones and in the tobacco area for materialswhich provide woody, peppery and citrusy aroma and taste nuances tosmoking tobacco prior to smoking and imparts a sweet, citrusy characterto smoke flavor on smoking in the smoking tobacco compositions and inthe smoking tobacco article components.

Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)" Volume II,published by the author 1969 discloses at Monograph 1932, ten-carbonatom containing alkylidene methyl cycloalkenones, specifically,3-methyl-5-n-butylidene cyclopenten-2-one defined according to thestructure: ##STR3## Arctander describes this compound as having a warm,caramellic, fruity odor reminiscent of strawberry; a sweet, fruity"cooked" strawberry flavor in dilutions below 20 ppm; and indicates thatthe ketone has been used and is "still used" to some extent in flavorcompositions, rarely in perfumes. Arctander further states that thiscompound could be used as a modifier in fruity, floral bases since itblends excellently with the jasmone derivatives and isomers and alsowith the ionones.

Although substituted alkyl isopropyl cyclohexenones are known in theprior art, the disclosure of these substituted alkyl isopropylcyclohexeneones does not include the utilization thereof in perfumeryand, furthermore, does not include processes for producing thesubstituted alkyl isopropyl cyclohexenones of our invention. Thus,Wiemann, et al and Riand and Brun in the references:

(i) Wiemann, et al, Ann. Chim., 1972, Volume 7, pages 399-499, title:"Contributions a L'Etude des Mechanismes de Condensations Catalytiquesde Cetones β-Alkyl α-Ethyleniques en Milieu Heterogene et en PhaseVapeur. Etudes Spectrographiques IR, UV, RMN".

(ii) Riand and Brun, Bulletin de la Societe Chimique de France, 1976,Nos. 3-4 (combined) pages 557-562 inclusive, title: "No.105--Spectrometrie de Masse. II--Fragmentations Induites par ImpactElectronique de Cyclohexenones".

disclose the compounds having the structures: ##STR4## produced bydimerization of the compound having the structure: ##STR5## overmagnesium oxide dimerization catalyst in the gas phase according to thereaction: ##STR6##

The prior art process of Riand and Brun or Wiemann, et al does notutilize a liquid phase dimerization and does not utilize the catalystsystems of our invention. Thus, the reaction mixture produced by Riandand Brun or Wiemann does not give rise to the same mixture of compoundsas our invention and, furthermore, carrying out the process of ourinvention, we produce certain novel compounds not heretofore produced.

Unsaturated cyclic ketones with unsaturated alkylene and alkylidene sidechains are known in the field of perfumery but these compounds aredifferent in kind in structure from the structures of the compounds ofthe present invention. Thus, piperitenone having the structure: ##STR7##is disclosed by Arctander, "Perfume and Flavor Chemicals (AromaChemicals)" at Monograph No. 2628 to have a powerful, sharp, minty,bitter-herbaceous odor of moderate intensity. Arctander further statesat Monograph No. 2629 that isopiperitenone having the structure:##STR8## has a powerful, diffusive odor sweeter than that ofpiperitenone but equally minty, penetrating and of moderate tenacity. AtMonograph No. 579, Arctander describes d-carvone having the structure:##STR9## as having a warm, herbaceous, bread-like, spicey and slightlyfloral odor reminiscent of dill seed. Arctander also describes 1-carvoneat Monograph No. 580 of Volume 1 as having a warm, herbaceous,bread-like, penetrating and diffusive odor, somewhat spicey, in extremedilution also floral, over-all reminiscent of spearmint oil (rectified).1-carvone has the structure: ##STR10##

Nothing in the prior art discloses the novel and useful and unexpectedlyadvantageous organoleptic utilities of our invention and nothing in theprior art discloses or renders obvious the novel compounds of ourinvention or the novel producty-by-process of our invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example A whereinthe mixture defined according to the structure: ##STR11## is producedwherein in the mixture in each of the molecules one of the dashed linesis a carbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond and the molecules are different.

FIG. 2 is the NMR spectrum for the reaction product of Example Acontaining a mixture of compounds defined according to the structure:##STR12## wherein in the mixture in each of the molecules one of thedashed lines in a carbon-carbon double bond and the other of the dashedlines is a carbon-carbon single bond and the components of the mixtureare different.

FIG. 3 is the infra-red spectrum for the reaction product of Example Acontaining the compounds defined according to the structure: ##STR13##wherein in the mixture in each of molecules, one of the dashed lines isa carbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond and the compounds are different.

FIG. 4 is the GLC profile for the crude reaction product producedaccording to Example I containing a mixture of compounds definedaccording to the structures: ##STR14## as well as the mixture ofcompounds which is the starting material for producing said compoundsdefined according to the structure: ##STR15##

FIG. 5 is the GLC profile for the bulked distillation fractions 11-19 ofthe distillation product of the reaction product of Example I containingthe compounds having the structures: ##STR16##

FIG. 6 is the NMR spectrum for Peak 1 (indicated by the referencenumeral "2" on the GLC profile of FIG. 4, supra). The compound of Peak 1has the structure: ##STR17##

FIG. 7 is the infra-red spectrum for the compound of Peak 1 of the GLCprofile of FIG. 4 having the structure: ##STR18##

FIG. 8 is the NMR spectrum for Peak 2 of the GLC profile of FIG. 4 whichis indicated by reference numeral "3" on said FIG. 4. Peak 2 signifiesthe compound having the structure: ##STR19##

FIG. 9 is the infra-red spectrum for Peak 2 of the GLC profile of FIG.4, containing the compound having the structure: ##STR20##

FIG. 10 is the NMR spectrum for Peak 3 of the GLC profile of FIG. 4,with Peak 3 being signified by the reference numeral "4". Peak 3contains the compound having the structure: ##STR21##

FIG. 11 is the infra-red spectrum for Peak 3 of the GLC profile of FIG.4 which signifies the compound having the structure: ##STR22##

FIG. 12 is the NMR spectrum for Peak 4A of the GLC profile of FIG. 4which signifies the compound having the structure: ##STR23## Peak 4A isindicated on FIG. 4 by reference numeral "5".

FIG. 13 is the infra-red spectrum for Peak 4A of the GLC profile of FIG.4 signifying the compound having the structure: ##STR24##

FIG. 14 is the NMR spectrum for Peak 4B of the GLC profile of FIG. 4signifying the compound having the structure: ##STR25## or the compoundhaving the structure: ##STR26## Peak 4B is indicated on FIG. 4 to havethe reference numeral "5".

FIG. 15 is the infra-red spectrum for Peak 4B of the GLC profile of FIG.4 which signifies one of the compounds having the structures: ##STR27##Peak 4B is shown by reference numeral "5" on FIG. 4.

FIG. 16 is the NMR spectrum for Peak 5 of the GLC profile of FIG. 4signifying the compounds having the structures: ##STR28## Peak 5 isindicated by the reference numeral "6" on FIG. 4.

FIG. 17 is the infra-red spectrum for Peak 5 of the GLC profile of FIG.4 signifying the compounds having the structures: ##STR29## Peak 5 isindicated on FIG. 4 by reference numeral "6".

FIG. 18 is the GLC profile for bulked fractions 11-19 of Example Iindicating groups of trapped peaks for organoleptic evaluations thusly:

(i) Group "A" is the combination of Peaks 1, 2 and 3;

(ii) Group "B" is Peak 4;

(iii) Group "C" is Peak 5.

FIG. 19A is the GLC profile for the reaction product of Example II.

FIG. 19B is the GLC profile for the distillation product, bulkedfractions 7-17 of the reaction product of Example II.

FIG. 20 is the GLC profile for the reaction product of Example IIIcontaining the compounds having the structures: ##STR30##

FIG. 21 is the NMR spectrum for Peak 1 of the GLC profile of FIG. 20containing the compounds having the structures: ##STR31##

FIG. 22 is the infra-red spectrum for Peak 1 of the GLC profile of FIG.20 containing the compounds having the structures: ##STR32## Peak 1 issignified by reference numeral "20" on FIG. 20.

FIG. 23 is the NMR spectrum for Peak 2 of the GLC profile of FIG. 20containing the compounds having the structures: ##STR33## Peak 2 isindicated by reference numeral "21" on FIG. 20.

FIG. 24 is the infra-red spectrum for Peak 2 of the GLC profile of FIG.20 containing the compounds having the structures: ##STR34##

FIG. 25 is the NMR spectrum for Peak 3 of the GLC profile of FIG. 20 forthe reaction product of Example III. Peak 3 contains the compoundshaving the structures: ##STR35## Peak 3 is indicated by referencenumeral "22" on FIG. 20.

FIG. 26 is the infra-red spectrum for Peak 3 of the GLC profile of FIG.20 containing the compounds having the structures: ##STR36##

FIG. 27 is the GLC profile for the reaction product of Example IV(B).

FIG. 28 is the GLC profile for the reaction product of Example IV(C).

FIG. 29 is the GLC profile for the reaction product of Example IV(D).

FIG. 30 is the GLC profile for the reaction product of Example IV(E).

FIG. 31 is the GLC profile for the reaction product of Example IV(F).

FIG. 32 is the GLC profile for the reaction product of Example IV(G).

FIG. 33 is the GLC profile for the reaction product of Example IV(H).

FIG. 34 is the GLC profile for the reaction product of Example IV(J).

FIG. 35 is the GLC profile for the reaction product of Example IV(K).

FIG. 36 is the GLC profile for the reaction product of Example IV(L).

FIG. 37 is the GLC profile for the reaction product of Example IV(M).

FIG. 38A is the GLC profile for the reaction product of Example V(conditions: barium hydroxide catalyst; methanol solvent; temperature:70° C.; dimerization product of reaction product of isobutyraldehyde andacetone).

FIG. 38B is the GLC profile for bulked fractions 8-15 of thedistillation product of the reaction product of Example V.

FIG. 39A is the GLC profile for the reaction product (after 2 hours) ofExample VI (conditions: KOH catalyst; methanol solvent; reactiontemperature: 50° C.; dimerization product of reaction product ofisobutyraldehyde and acetone).

FIG. 39B is the GLC profile for bulked fractions 7-20 of thedistillation product of the reaction product of Example VI.

FIG. 40A is the GLC profile for the reaction product of Example VII(conditions: sodium hydroxide catalyst; methanol solvent; reactiontemperature: 30° C.; dimerization product of reaction product ofisobutyraldehyde and acetone).

FIG. 40B is the GLC profile for bulked fractions 6-16 of thedistillation product of the reaction product of Example VII.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 4 is the GLC profile for the crude reaction product producedaccording to Example I.

The conditions are Carbowax column operated at 200° C., isothermal.

The Peak indicated by the reference numeral "1" is the starting materialwhich is a mixture of compounds defined according to the structure:##STR37## wherein in the mixture in each of the molecules one of thedashed lines is a carbon-carbon double bond and the other of the dashedlines is a carbon-carbon single bond and the molecules are different.

The Peaks indicated by reference numerals "2", "3", "4", "5" and "6"represent products produced by means of the dimerization of the compounddefined according to the structure: ##STR38##

Thus, the Peak indicated by reference numeral "2" is "Peak 1" which isthe compound having the structure: ##STR39##

The Peak indicated according to reference numeral "3" is "Peak 2" havingthe structure: ##STR40##

"Peak 3" indicated by reference numeral "4" has the structure: ##STR41##

The Peak signified by the reference numeral "5" is a combination ofPeaks 4A and 4B. Peak 4A is the compound having the structure: ##STR42##Peak 4B is either the compound having the structure: Peak 4B is eitherthe compound having the structure: ##STR43## and/or the compound havingthe structure: ##STR44##

The Peak indicated by reference numeral "6" is Peak 5 which is thecompound having the structure: ##STR45## and/or the compound having thestructure:

FIG. 5 is the GLC profile for bulked distillation fractions 11-19 of thedistillation product of the reaction product of Example I.

The Peak indicated by reference numeral "7" is Peak 1 which is thecompound having the structure: ##STR46##

The Peak indicated by reference numeral "8" is Peak 2 having thestructure: ##STR47##

The Peak indicated by reference numeral "9" is Peak 3 having thestructure: ##STR48##

The Peak indicated by reference numeral "10" is Peak 4A having thestructure: ##STR49##

The Peak indicated by reference numeral "11" is Peak 4B having thestructure: ##STR50##

The Peak indicated by reference numeral "12" is Peak 5 having thestructure: ##STR51##

FIG. 18 is the GLC profile for bulked fractions 11-19 of thedistillation product of the reaction product of Example I wherein thePeaks are grouped into three groupings:

Group "A" which is Peaks 1, 2 and 3 indicated by reference numerals"13", "14" and "15"

Group "B" which is Peak 4 indicated by reference numeral "17" and

Group "C" which is Peak 5 indicated by reference numeral "19".

In Group "A", the peak indicated by reference numeral "13" is Peak 1having the structure: ##STR52##

Peak 2 is indicated by reference numeral "14" and has the structure:##STR53##

Peak 3 is indicated by reference numeral "15" and has the structure:##STR54##

Peak 4 is indicated by reference numerals "17" and "18" and have thestructures: ##STR55##

Peak 5 is indicated by reference numeral "19" and has the structure:##STR56##

FIG. 20 is the GLC profile for the reaction product of Example III(conditions: SE-30 column programmed at 200° C., isothermal).

The Peak indicated by reference numeral "20" is Peak 1 having thestructure: ##STR57##

The Peak indicated by reference numeral "21" is Peak 2 having thestructure: ##STR58##

The Peak indicated by reference numeral "22" is Peak 3 having thestructure: ##STR59##

THE INVENTION

It has now been determined that certain substituted methyl isopropylcyclohexenones defined according to the structure: ##STR60## wherein oneof the dashed lines represents a carbon-carbon double bond and the otherof the dashed lines represents a carbon-carbon single bond; wherein R₄represents methyl or ethyl; wherein one of R₁, R₂ and R₃ represents2-methyl-1-propenyl or 2-methyl-1-propylidenyl; and the other of R₁, R₂and R₃ represent hydrogen; with the provisos that:

(i) when the dashed line at the 3-4 position is a double bond, then R₃is hydrogen or 2-methyl-1-propenyl;

(ii) when the dashed line at the 2-3 position is a double bond, then R₂is hydrogen or 2-methyl-1-propenyl;

(iii) when R₄ is ethyl, then R₂ is methyl and the double bond is at the2-3 position; and

(iv) when R₄ is methyl, then R₂ is hydrogen; 2-methyl-1-propenyl or2-methyl-1-propylidenyl;

with the members of said genus being novel compounds when R₄ is ethyl orwhen R₄ is methyl and the double bond is at the 3-4 position or when R₄is methyl and the double bond is at the 2-3 position with R₃ beinghydrogen.

Briefly, our invention contemplates augmenting or enhancing the flavorsand/or fragrances of such consumable materials as perfumes, perfumedarticles, colognes, smoking tobaccos and smoking tobacco articles byadding thereto a small but effective amount of at least one of thecompounds defined according to the structure: ##STR61## wherein thedashed lines and R₁, R₂, R₃ and R₄ are as defined supra.

Also contemplated within the scope of our invention are processes forpreparing such compounds and the products produced by such processes.These processes involve the dimerization of the mixture of compoundsdefined according to the structure: ##STR62## wherein R₄ ' representshydrogen or methyl and in the mixture one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond, using a catalyst which is either an alkalimetal hydroxide, an alkaline earth metal hydroxide, aluminum chloride,sulfuric acid, or pyrrolidinium acetate in the presence of an inertsolvent such as ethanol, methanol, isopropanol, n-propanol, n-hexane, ortoluene. The process can be carried out by producing the compoundsdefined according to the structure: ##STR63## in situ by carrying outthe aldol condensation of isobutyraldehyde having the structure:##STR64## with the ketone having the structure: ##STR65## wherein R₄ "is hydrogen or methyl using the same solvent system as defined above andthe same catalyst range as defined above.

The substituted methyl isopropyl cyclohexenone derivatives of ourinvention augment or enhance peppery, sweaty, guiacwood-like, green,burnt grass-like, vetiver-like, sandalwood-like, fresh, floral, citrusyand spicy aromas with sauge sclaree topnotes and musky undertonesinsofar as augmenting or enhancing the aroma of perfumes, perfumedarticles and colognes of our invention.

The substituted methyl isopropyl cyclohexenones of our invention alsoaugment or enhance, prior to smoking, the woody, peppery and citrusyaroma and taste nuances of smoking tobacco and smoking tobacco articlecomponents and, on smoking, impart a sweet, citrusy character to smokeflavor in smoking tobaccos and components of smoking tobacco articles inthe main stream and in the side stream.

As stated supra, the reaction of our invention may be carried out byeither (a) dimerization of the ketone mixture defined according to thestructure: ##STR66## wherein in the mixture, one of the dashed linesrepresents a carbon-carbon double bond and the other of the dashed linesrepresents a carbon-carbon single bond and R₄ ' represents hydrogen ormethyl or (b) by forming the mixture of ketones defined according to thestructure: ##STR67## in situ by carrying out the reaction ofisobutyraldehyde with the ketone defined according to the structure:##STR68##

When carrying out the aforementioned reaction "in situ", this reactioncan be shown thusly: ##STR69## wherein R₁, R₂, R₃, R₄, R₄ ', R₄ " andthe dashed lines are defined as above.

Whether carrying out the reaction in situ or carrying out thedimerization starting with the ketone mixture defined according to thestructure: ##STR70## the reaction is carried out at a temperature in therange of from about 25° C. up to about 120° C. at atmospheric pressurein the presence of:

(a) a solvent which can be hydrocarbon such as n-hexane or toluene; aninert alkanol such as methyl alcohol, ethyl alcohol or isopropylalcohol; and

(b) a catalyst which is either acidic or basic such as an alkali metalhydroxide such as potassium hydroxide or sodium hydroxide; an alkalineearth metal hydroxide such as barium hydroxide; aluminum chloride; or anamphoteric catalyst such as pyrrolidinium acetate defined according tothe structure: ##STR71##

As will be seen by an examination of the GLC profiles in the figures assummarized supra, the isomer ratios of the reaction product mixturedefined according to the structure: ##STR72## will vary and depend uponthe following reaction variables: (a) temperature of reaction;

(b) time of reaction;

(c) nature of catalyst;

(d) concentration of catalyst;

(e) nature of solvent;

(f) concentration of reactant in solvent;

(g) ratio of catalyst to reactant.

When carrying out the reaction between the isobutyraldehyde and ketonedefined according to the structure: ##STR73## in situ, the mole ratio ofisobutyraldehyde:ketone having the structure: ##STR74## may vary from1.5:0.5 up to 0.5:1.5 of isobutyraldehyde:ketone. The reactiontemperature range may vary from about 25° C. up to about 120° C. and ispreferably the temperature at which the reaction mass will reflux atatmospheric pressure. Thus, when carrying out the reaction using amethyl alcohol catalyst wherein the reactant concentration is 4 kg. perliter using methanol, the reaction temperature is maintained at 50°-52°C.

The concentration of catalyst in the reaction mass may vary from about50 grams per liter up to about 400 grams per liter. The nature of thesolvent may vary as set forth above with the preferred solvents beingmethanol, ethanol and isopropyl alcohol. The nature of the catalyst mayvary as set forth above with the preferred catalysts being sodiumhydroxide, potassium hydroxide and barium hydroxide.

Certain of the substituted methyl isopropyl cyclohexenones of ourinvention are novel compounds per se and these are defined according tothe structure: ##STR75## wherein one of the dashed lines represents acarbon-carbon double bond and the other of the dashed lines represents acarbon-carbon single bond; wherein R₄ represents methyl or ethyl;wherein one of R₁, R₂ and R₃ represents 2-methyl-1-propenyl or2-methyl-1-propylidenyl; and the other of R₁, R₂ and R₃ representhydrogen; with the provisos that:

(i) when the dashed line at the 3-4 position is a double bond, then R₃is hydrogen or 2-methyl-1-propenyl;

(ii) when the dashed line at the 2-3 position is a double bond, then R₂is hydrogen or 2-methyl-1-propenyl;

(iii) when R₄ is ethyl, then R₂ is methyl and the double bond is at the2-3 position; and

(iv) when R₄ is methyl, then R₂ is hydrogen; 2-methyl-1-propenyl or2-methyl-1-propylidenyl;

with the members of said genus being novel compounds when R₄ is ethyl orwhen R₄ is methyl and the double bond is at the 3-4 position or when R₄is methyl and the double bond is at the 2-3 position with R₃ beinghydrogen. Thus, for example, the compounds defined according to thestructures: ##STR76## are novel compounds. On the other hand, thecompounds defined according to the structures: ##STR77## are the onlycompounds of the genus: ##STR78## which are not novel.

The substituted methyl isopropyl cyclohexenones of our invention can beobtained in pure form or in substantially pure form by conventionalpurification techniques. Thus, the products can be purified and/orisolated by distillation, extraction, crystallization, preparativechromatographic techniques (column chromatography and vapor phasechromatography) and the like. It has been found desirable to purify thesubstituted methyl isopropyl cyclohexenone derivatives of our inventionby fractional distillation in vacuo.

The substituted methyl isopropyl cyclohexenone derivatives of ourinvention can be used alone or in combination to contribute peppery,sweaty, guiacwood-like, green, burnt grass, vetiver-like,sandalwood-like, fresh, floral, citrusy and spicy aroma nuances withsauge sclaree topnotes and musky undertones to perfumes, perfumedarticles and colognes.

As olfactory agents, the substituted methyl isopropyl cyclohexenones ofour invention can be formulated into or used as components of a "perfumecomposition" or can be used as components of a "perfumed article" or theperfume composition may be added to "perfumed articles".

The term "perfume composition" is used herein to mean a mixture oforganic compounds including, for example, alcohols, aldehydes, ketones(other than the ketones of our invention), nitriles, ethers, lactones,natural essential oils, synthetic essential oils and frequentlyhydrocarbons which are admixed so that the combined odors of theindividual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain: (a) the main note or the "bouquet"or foundation stone of the composition; (b) modifiers which round offand accompany the main note; (c) fixatives which include odoroussubstances which lend a particular note to the perfume throughout allstages of evaporation and substances which retard evaporation and (d)topnotes which are usually low-boiling, fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum total of the effects of each of theingredients and possibly even more than the sum total of each of theeffects of each of the ingredients if there exists synergism amongst theingredients. Thus, the individual compounds of this invention ormixtures thereof can be used to alter, augment or enhance the aromacharacteristics of a perfume composition, for example, by highlightingor moderating the olfactory reaction contributed by another ingredientin the composition.

The amount of the substituted methyl isopropyl cyclohexenone derivativesof this invention which will be effective in perfume compositionsdepends on many factors, including the other ingredients, their amountsand the effects which are desired. It has been found that perfumecompositions containing as little as 0.05% of the methyl isopropylcyclohexenone derivatives of this invention, or even less, can be usedto impart an interesting peppery, sweaty, guiacwood-like, green, burntgrass-like, vetiver-like, sandalwood-like, fresh, floral, citrusy and/orspicy aroma profile with sauge sclaree topnotes and musky undertones tosoaps, liquid and solid cationic, anionic, nonionic and zwitterionicdetergents, cosmetic powders, liquid and solid fabric softeners, fabricsoftener articles, optical brightener compositions and other products.The amount employed can range up to 50% or higher and will depend onconsiderations of cost, nature of the end product and the effect desiredon the finished product and particular fragrance sought.

The substituted methyl isopropyl cyclohexenone derivatives of thisinvention can be used alone or in a perfume composition as an olfactorycomponent in detergents and soaps, space odorants and deodorants;perfumes; colognes, toilet waters; bath salts; hair preparations such aslacquers, brilliantines, pomades and shampoos; cosmetic preparationssuch as creams, deodorants, hand lotions and sun screens; powder such astalcs, dusting powders, face powders and the like. When used as anolfactory component of a perfumed article, as little as 0.01% of one ormore of the substituted methyl isopropyl cyclohexenone derivatives ofour invention will suffice to impart an interesting peppery, sweaty,guiacwood-like, green, burnt grass-like, vetiver-like, sandalwood-like,fresh, floral, citrusy and/or spicy aroma with sauge sclaree topnotesand musky undertones. Generally, no more than 0.5% (by weight of theperfumed article) is required. Thus, the range of use of the substitutedmethyl isopropyl cyclohexenones of our invention in perfumed articles is0.01% up to 0.5% and the use in perfume compositions per se is from0.05% to 50% of the methyl isopropyl cyclohexenones of our invention.

In addition, the perfume composition can contain a vehicle or carrierfor the substituted methyl isopropyl cyclohexenones of our inventiontaken alone or taken together with other ingredients. The vehicle can bea liquid such as an alcohol such as ethanol, a glycol such as propyleneglycol or the like. The carrier can be an absorbent solid such as a gum(e.g. gum arabic or guar gum or xanthan gum) or components forencapsulating the composition such as gelatin (as by coacervation) whichcan be used to form a capsule wall surrounding the perfume oil, or aurea formaldehyde resin which is formed by polymerization to form acapsule wall surrounding the perfume oil.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor includingmethods of making the same which overcome problems heretoforeencountered in the creation or enhancement of specific desired woody,peppery and citrusy notes prior to smoking or sweet, citrusy notes onsmoking both in the main stream and in the side stream. Such notes bothprior to and on smoking in both the main stream and the side stream maynow be readily controlled and maintained at the desired uniform levelregardless of variations in the tobacco components of the blend; or thenature of the filter used in conjunction with the smoking tobaccoarticle.

This invention further provides improved tobacco additives and additivesfor materials used in fabrication of tobacco articles (particularlysmoking tobacco articles) and methods whereby desirable woody, pepperyand citrusy notes prior to smoking and sweet, citrusy notes on smokingmay be imparted to smoking tobacco compositions and smoking tobaccoproducts and may be readily varied and controlled to produce the desireduniform flavor and characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g. dried lettuce leaves)an aroma and flavor additive containing as an active ingredient one ormore of the substituted methyl isopropyl cyclohexenone derivatives ofour invention.

In addition to the substituted methyl isopropyl cyclohexenones of ourinvention, other flavoring and aroma additives may be added to thesmoking tobacco material or substitute therefor either separately or inadmixture with one or more of the substituted methyl isopropylcyclohexenone derivatives of our invention thusly:

I. Synthetic materials

Beta-methylcinnamaldehyde

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate

2-hexen-1-ol;

2-methyl-5-isopropyl-1,3-nonadiene-8 -one;

2-methyl-5-isopropylacetophenone;

2-hydroxy-2,5,5,8α-tetramethyl-1-(2-hydroxyethyl)decahydronaphthalene;

Dodecahydro-3α,6,6,9α-tetramethylnaphthol(2,1-β-furan;

4-hydroxyhexenoic acid, gamma-lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil;

Origanum oil.

An aroma and flavoring concentrate containing one or more of thesubstituted methyl isopropyl cyclohexenone derivatives of our inventionand, if desired, one or more of the above indicated additional flavoringadditives may be added to the smoking tobacco material, to the filter orto the leaf or paper wrapper or to a filter which is part of the smokingarticle. The smoking tobacco material may be shredded, cured, cased andblended tobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g. lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste, butinsofar as enhancement or the imparting of woody, peppery and/or citrusyand sweet notes prior to and on smoking in both the main stream and theside stream, we have found that satisfactory results are obtained if theproportion by weight of the sum total of the substituted methylisopropyl cyclohexenones to smoking tobacco material is between 50 ppmand 2,500 ppm (0.005%-0.25%) of the active ingredients to the smokingtobacco material. We have further found that satisfactory results areobtained if the proportions by weight of the sum total of substitutedmethyl isopropyl cyclohexenone derivatives used to flavoring material isbetween 0.05:1 and 0.50:1.

Any convenient method for incorporating the substituted methyl isopropylcyclohexenone derivatives in the tobacco product may be employed. Thus,the substituted methyl isopropyl cyclohexenone derivatives taken aloneor along with other flavoring additives may be dissolved in a suitablesolvent such as food grade ethanol, pentane, diethyl ether and/or othervolatile organic solvents and the resulting solution may either besprayed on the cured, cased and blended tobacco material; or the tobaccomaterial or filter may be dipped into such solution. Under certaincircumstances, a solution of one or more substituted methyl isopropylcyclohexenone derivatives taken alone or taken further together withother flavoring additives as set forth above may be applied by means ofa suitable applicator such as a brush or roller on the paper or leafwrapper for the smoking product or it may be applied to the filter byeither spraying or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have one or moresubstituted methyl isopropyl cyclohexenone derivatives of our inventionin excess of the amounts or concentrations above indicated so that whenblended with other tobaccos, the final product will have the percentagewithin the indicated range.

While our invention is particularly useful in the manufacture of smokingtobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, othertobacco products formed from sheeted tobacco dust or fines may also beused. As stated supra, the substituted methyl isopropyl cyclohexenonederivatives of our invention can be incorporated with material such asfilter tip materials, seam paste, packaging materials and the like whichare used along with the tobacco to form a product adapted for smoking.Further, the substituted methyl isopropyl cyclohexenone derivatives ofour invention can be added to certain tobacco substitutes of natural orsynthetic origin (e.g. dried lettuce leaves) and, accordingly, by theterm "tobacco" as used throughout this specification is meant anycomposition intended for human consumption by smoking or otherwise,whether composed of tobacco plant parts or substitute material or both.

It will thus be apparent that the substituted methyl isopropylcyclohexenone derivatives of our invention can be utilized to alter,modify, augment or enhance sensory properties, particularly organolepticproperties such as flavors and/or fragrances of a wide variety ofconsumable materials.

The following Example A serves to illustrate a method for producing aprecursor for producing the products of our invention (an aldolcondensate). The following Examples I-IV inclusive, serve to illustratethe processes for carrying out the chemical syntheses of the products ofour invention. The following Examples V et seq. set forth the uses ofthe products of Examples I-IV of our invention. The invention is to beconsidered restricted to these examples only as indicated in theappended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE A Preparation of 5-Methyl-Hexene-2-One Mixture ##STR79##

Into a 5 liter reaction flask equipped with stirrer, thermometer,condenser, addition funnel and heating mantle and fitted with a Soxhletapparatus containing a thimble filled with barium hydroxide (200 grams)is placed a mixture of 1.5 kg of isobutyraldehyde and 1.4 kg of acetone.

The reaction mass is refluxed and the resultant 5-methyl-hexene-2-onemixture is collected in the reaction flask for a period of 4 hours.

At the end of the 4 hour period, the reaction mass is stripped of excessreactants and 2.3 kg of 5-methyl-hexene-2-one compounds are collectedvia distillation at a temperature of 74° C. and a pressure of 0.8 mm/Hgpressure.

FIG. 1 is the GLC profile of the reaction product (conditions: Carbowaxcolumn operated at 200° C. isothermal).

FIG. 2 is the NMR spectrum for the reaction product collected viadistillation at the temperature of 74° C. and 0.8 mm/Hg pressure.

FIG. 3 is the infra-red spectrum for the resulting product which is amixture of compounds defined according to the structure: ##STR80##wherein in the mixture, in each of the molecules, one of the dashedlines is a carbon-carbon double bond and the other of the dashed linesis a carbon-carbon single bond and the molecules of the mixture aredifferent.

EXAMPLE I Dimerization of 5-Methyl-Hexene-2-One Mixture ##STR81##wherein one of R₁, R₂ or R₃ is 2-methyl-1-propenyl having the structure:##STR82## or 2-methyl-1-propylidenyl having the structure: ##STR83## andthe other two of R₁, R₂ or R₃ is hydrogen; and wherein in the mixture,in each of the molecules of the mixture, one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond and wherein the molecules of the mixture arerepresented thusly: ##STR84##

Into a 5 liter reaction flask equipped with stirrer, thermometer,condenser, addition funnel, heating mantle, cooling bath andTherm-o-watch apparatus is placed 100 grams of potassium hydroxide. 500ml of methanol is placed in an addition funnel. Over a period of 10minutes, the methanol is added to the KOH. After the methanol is mixedwith the KOH, the resulting mixture is heated to 50° C. and over aperiod of 1 hour, the 5-methyl-hexene-2-one mixture (2 kg) producedaccording to Example A (boiling point 74° C. at 0.8 mm/Hg pressure) isadded to the reaction mass while maintaining the reaction mass at50°-55° C. At the end of the addition, the reaction mass is stirred fora period of 1.5 hours at 50°-51° C. The reaction mass is then added totwo liters of water and the resulting organic layer is washed with twoliters of water to a pH of 7. The organic layer is then distilled on a24" Goodloe column to yield 917.2 grams of product and the fractionsresulting from this distillation are as follows:

    ______________________________________                                               Vapor    Liquid                 Weight of                              Fraction                                                                             Temp.    Temp.    Pressure                                                                             Reflux Fraction                               Number (°C.)                                                                           (°C.)                                                                           mm/Hg  Ratio  (grams)                                ______________________________________                                         1     60/85    147/143  0.4/.25                                                                              9:1    47.2                                    2     92       140      0.25   9:1    44.5                                    3     98       140      0.30   9:1    36.3                                    4     84       139      0.22   9:1    44.7                                    5     88       141      0.40   9:1    39.9                                    6     88       142      0.40   9:1    42.0                                    7     88/95    140/141  0.4/0.4                                                                              9:1    41.0                                    8     104      145      0.7    9:1    45.7                                    9     101      148      0.6    9:1    43.1                                   10     103      148      0.5    9:1    39.9                                   11     102      148      0.4    9:1    48.2                                   12     102      148      0.4    9:1    49.8                                   13     103      149      0.4    9:1    41.2                                   14     104      150      0.4    9:1    24.8                                   15     103      150      0.4    9:1    47.0                                   16     92/100   145/147  0.4/0.4                                                                              2:1    36.4                                   17     93       142      0.4    2:1    48.7                                   18     93       143      0.4    2:1    41.6                                   19     93       146      0.4    2:1    45.1                                   20     93       150      0.4    2:1    38.1                                   21     95       195      0.5    2:1    39.6                                   ______________________________________                                    

Fractions 7-22 are bulked for the purposes of organoleptic evaluation.From an aroma standpoint, bulked fractions 7-22 have a peppery,guiacwood-like, vetiver-like, sandalwood-like aroma with a sauge sclareetopnote and a musky undertone.

FIG. 4 is the GLC profile for the crude reaction product (GLCconditions: Carbowax column operated at 200° C. isothermal).

The Peak on the GLC profile indicated by the reference numeral "1"represents the starting material having the structure: ##STR85## amixture, wherein in the mixture in one of the molecules one of thedashed lines is a carbon-carbon double bond and the other of the dashedlines is a carbon-carbon single bond and in the other of the molecules,the other of the dashed lines is a carbon-carbon double bond.

The Peak indicated by the reference numeral "2", Peak, 1, has thestructure: ##STR86##

The Peak indicated by the reference numeral "3", Peak 2, has thestructure: ##STR87##

The Peak indicated by the reference numeral "4", Peak 3, has thestructure: ##STR88##

The Group of Peaks indicated by the reference numeral "5" is a mixtureof Peaks 4A and 4B. Peak 4A has the structure: ##STR89## Peak 4B has thestructure: ##STR90##

The Peak indicated by reference numeral "6" is Peak 5 and it has thestructure: ##STR91##

FIG. 5 is the GLC profile for the bulked distillation fractions 11-19 ofthe following distillation of the foregoing reaction product.

The Peak indicated by reference numeral "7" is Peak 1 having thestructure: ##STR92##

The Peak indicated by reference numeral "8" is Peak 2 having thestructure: ##STR93##

The Peak indicated by reference numeral "9" is Peak 3 having thestructure: ##STR94##

The Peak indicated by reference numeral "10" is Peak 4A having thestructure: ##STR95##

The Peak indicated by reference numeral "11" is Peak 4B having thestructure: ##STR96##

The Peak indicated by reference numeral "12" is Peak 5 having thestructure: ##STR97##

FIG. 6 is the NMR spectrum for Peak 1 having the structure: ##STR98##

FIG. 7 is the IR spectrum for Peak 1 of the foregoing GLC profile havingthe structure: ##STR99##

FIG. 8 is the NMR spectrum for Peak 2 of the foregoing GLC profilehaving the structure: ##STR100##

FIG. 9 is the infra-red spectrum for Peak 2 of the foregoing GLC profilehaving the structure: ##STR101##

FIG. 10 is the NMR spectrum for Peak 3 of the foregoing GLC profilehaving the structure: ##STR102##

FIG. 11 is the infra-red spectrum for Peak 3 of the foregoing GLCprofile having the structure: ##STR103##

FIG. 12 is the NMR spectrum for Peak 4A of the foregoing GLC profilehaving the structure: ##STR104##

FIG. 13 is the infra-red spectrum for Peak 4A of the foregoing GLCprofile having the structure: ##STR105##

FIG. 14 is the NMR spectrum for Peak 4B of the foregoing GLC profilehaving the structure: ##STR106##

FIG. 15 is the infra-red spectrum for Peak 4B of the foregoing GLCprofile having the structure: ##STR107##

FIG. 16 is the NMR spectrum for Peak 5 of the foregoing GLC profilehaving the structure: ##STR108##

FIG. 17 is the infra-red spectrum for Peak 5 of the foregoing GLCprofile having the structure: ##STR109##

FIG. 18 is the GLC profile for bulked fractions 11-19.

The Peaks of the GLC profile are grouped as follows:

Group "A" is a mixture of Peaks 1, 2 and 3. Group "A" has a sweaty,burnt grass aroma.

Group "B" is a mixture of Peaks 4A and 4B. Group "B" has an intensepeppery, guiacwood, vetiver, sandalwood-like aroma with a sauge sclareetopnote and a musky undertone.

Group "C" is Peak 5. Group "C" has a green, vetiver aroma.

EXAMPLE II Preparation of Substituted Methyl Isopropyl CyclohexenoneMixture ##STR110## wherein one of the dashed lines represents acarbon-carbon double bond and the other of the dashed lines represents acarbon-carbon single bond and wherein one of R₁, R₂ and R₃ is2-methyl-1-isopropylidenyl having the structure: ##STR111## or2-methyl-1-isopropenyl having the structure: ##STR112## and the other ofR₁, R₂ and R₃ represents hydrogen in each of the components of themixture.

Into a 12 liter reaction flask equipped with stirrer, thermometer,reflux condenser, dropping funnel, heating mantle and cooling bath isplaced 1,160 grams of acetone, 250 grams of potassium hydroxide and1,000 ml of anhydrous methyl alcohol. The reaction mass is heated to 50°C. and while maintaining the reaction mass at 50°-52° C., over a periodof 1 hour is placed 1 kg of isobutyraldehyde. The reaction mass is thenheated for a period of 2 hours at 52° C. At the end of the reaction, thereaction mass is poured into two liters of 10% salt solution. Theresulting aqueous mixture is washed with 1 liter of toluene. The tolueneextract is then washed with three 1-liter portions of water to a pH of7. The resulting reaction product is evaporated and then distilledyielding the following fractions:

    ______________________________________                                               Vapor    Liquid                 Weight of                              Fraction                                                                             Temp.    Temp.    Pressure                                                                             Reflux Fraction                               Number (°C.)                                                                           (°C.)                                                                           mm/Hg. Ratio  (grams)                                ______________________________________                                         1     55/71    125/127  1.0/1.0                                                                              9:1/9:1                                                                              24.2                                    2     73       124      1.0    9:1    33.2                                    3     74       125      0.8    9:1    33.0                                    4     87       125      0.8    9:1    43.9                                    5     91       126      0.8    9:1    23.7                                    6     95       130      0.8    100%   43.5                                    7     95       130      0.8    100%   43.4                                    8     95       132      0.8    100%   45.4                                    9     95       132      0.8    100%   51.3                                   10     95       133      0.8    100%   43.1                                   11     95       133      0.8    100%   42.9                                   12     95       133      0.8    100%   41.0                                   13     97       134      0.8    100%   38.5                                   14     97       134      0.8    100%   43.6                                   15     97       135      0.8    100%   44.9                                   16     97       137      0.8    100%   43.8                                   17     97       138      0.8    100%   44.2                                   18     97       142      0.8    100%   44.6                                   19     97       146      0.8    100%   46.6                                   20     100      162      0.8    100%   39.8                                   21     100      167      0.8    100%    8.0                                   ______________________________________                                    

Fractions 2-6 are bulked and evaluated as having a peppery,guiacwood-like, vetiver-like aroma with sauge sclaree topnotes.

FIG. 19A is the GLC profile of the reaction product subsequent to thereaction but prior to distillation.

FIG. 19B is the GLC profile of bulked fractions 7-17. It is bulkedfractions 7-17 which have the peppery, guiacwood-like, vetiver aromawith the sauge sclaree topnotes.

EXAMPLE III Preparation of Substituted Methyl Isopropyl CyclohexenoneMixture from Methyl Ethyl Ketone and Isobutyraldehyde ##STR113## whereinone of R₆ and R₇ in the resulting mixture is 2-methyl-1-propenyl and theother of R₆ or R₇ in the mixture is hydrogen.

Into a 12 liter reaction flask equipped with thermometer, stirrer,addition funnel, reflux condenser and heating mantle is placed 1,000 mlmethanol and 250 grams of potassium hydroxide. The resulting mixture isheated to 50° C. and over a five minute period, 1,200 grams of methylethyl ketone is added. While maintaining the reaction mixture at 50° C.over a period of 1 hour, 1,000 grams of isobutyraldehyde is added to thereaction mass. The reaction mass is then stirred at 50° C. for a periodof 1.5 hours. At the end of the 1.5 hour period, the reaction mass ispoured into 2,000 ml of water and extracted with 1 liter of toluene. Theresulting toluene extract is washed with water to a pH of 6-7. Theresulting material is then stripped of solvent and distilled in aGoodloe column yielding the following fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      Pressure                                                                             Fraction                                   Number   (°C.)                                                                          (°C.)                                                                             mm/Hg. (grams)                                    ______________________________________                                         1       35/217  112/127    2.4/2.4                                                                              17.8                                        2        78     137        1.4    43.9                                        3       104     147        1.0    44.1                                        4       108     148        1.0    40.0                                        5       111     150        0.8    45.5                                        6       111     150        0.7    43.9                                        7       112     150        1.0    44.4                                        8       108     150        0.5    45.1                                        9       108     150        0.4    46.6                                       10       107     149        0.5    57.1                                       11       105     148        0.4    45.8                                       12       104     147        0.4    46.4                                       13       103     147        0.4    46.7                                       14       103     149        0.4    47.4                                       15       105     151        0.4    47.7                                       16       108     154        0.6    47.4                                       17       105     154        0.4    46.2                                       18       107     155        0.6    47.7                                       19       112     165        0.6    52.5                                       20       113     167        0.4    46.9                                       21       120     176        0.4    42.7                                       22       124     182        0.4    41.2                                       23       128     191        0.6    31.0                                       24       135     250        0.5    30.5                                       ______________________________________                                    

Fractions 4-18 of the foregoing distillation fractions are bulked andevaluated from an organoleptic standpoint. Bulked fractions 4-18 have afresh, floral, citrus and spicy aroma.

FIG. 20 is the GLC profile of the reaction product prior todistillation.

Peak 1 or Peak 3 have the structures: ##STR114##

Peak 2 has the structures: ##STR115##

FIG. 21 is the NMR spectrum for Peak 1.

FIG. 22 is the IR spectrum for Peak 1 of the foregoing GLC profile.

FIG. 23 is the NMR spectrum for Peak 2 of the foregoing GLC profile.

FIG. 24 is the infra-red spectrum for Peak 2 of the foregoing GLCprofile.

FIG. 25 is the NMR spectrum for Peak 3 of the foregoing GLC profile.

FIG. 26 is the infra-red spectrum for Peak 3 of the foregoing GLCprofile.

EXAMPLES IV(A-M) Preparation of Substituted Methyl IsopropylCyclohexenone Mixtures Using Various Catalysts and Various Solvents##STR116## wherein one of R₁, R₂ and R₃ is hydrogen and the other of R₁,R₂ or R₃ is 2-methyl-1-propylidene or 2-methyl-1-propenyl having thestructures, respectively: ##STR117## and wherein one of the dashed linesrepresents a carbon-carbon double bond and where the other of the dashedlines represents a carbon-carbon single bond.

The following Table I summarizes the reaction conditions for the generalreaction procedure set forth below:

Into a 1 liter flask equipped with thermometer, stirrer, additionfunnel, reflux condenser and heating mantle is placed 200 ml of solventas specified in Table I below and 50 grams of catalyst as specified inTable I below. The resulting mixture is heated at a temperature asindicated in Table I below and to the mixture over a period of 10minutes is added 250 grams of 5-methyl-hexene-2-one mixture preparedaccording to Example A (boiling point 74° C. at 0.8 mm/Hg). Theresulting mixture is heated at a temperature as indicated in Table Ibelow for a period of 1 hour at the end of which period of time thereaction mass is poured into 500 ml water. The organic phase is thenwashed with water to a pH of 6-7 and a GLC profile is run in order toascertain the extent of product produced. in Table I set forth below, anindication is set forth whether product is produced or not. In each ofthe cases, the product produced is defined according to the genericstructure: ##STR118## which is a mixture wherein in the mixture, one ofR₁, R₂ and R₃ is 2-methyl-1-propenyl or 2-methyl-1-propylidenyl and theother of R₁, R₂ and R₃ is hydrogen and wherein one of the dashed linesrepresents a carbon-carbon double bond and the other of the dashed linesrepresents a carbon-carbon single bond.

                  TABLE I                                                         ______________________________________                                                                           Indication of                                                          Tem-   Product                                    Example                                                                              Catalyst    Solvent  perature                                                                             Formed                                     ______________________________________                                        IV(A)  sulfuric acid                                                                             toluene  110° C.                                                                       No products                                                                   produced                                   IV(B)  sodium      ethyl    50° C.                                                                        Product                                           hydroxide   alcohol         produced                                   IV(C)  potassium   methyl   65° C.                                                                        Product                                           hydroxide   alcohol         produced                                   IV(D)  barium      ethyl    78° C.                                                                        Product                                           hydroxide   alcohol         produced                                   IV(E)  aluminum    n-hexane 70° C.                                                                        Product                                           chloride                    produced                                   IV(F)  sulfuric acid                                                                             n-hexane 70° C.                                                                        Product                                                                       produced                                   IV(G)  sodium      ethyl    78° C.                                                                        Product                                           hydroxide   alcohol         produced                                   IV(H)  potassium   ethyl    78° C.                                                                        Product                                           hydroxide   alcohol         produced                                   IV(J)  potassium   methyl   30° C.                                                                        Product                                           hydroxide   alcohol         produced                                   IV(K)  sodium      isopropyl                                                                              82° C.                                                                        Product                                           hydroxide   alcohol         produced                                   IV(L)  barium      isopropyl                                                                              82° C.                                                                        Product                                           hydroxide   alcohol         produced                                   IV(M)  pyrrolidinium                                                                             methyl   65° C.                                                                        Product                                           acetate having                                                                            alcohol         produced                                          the structure:                                                          ##STR119##                                                                   ______________________________________                                    

FIG. 27 is the GLC profile for Example IV(B).

FIG. 28 is the GLC profile for Example IV(C).

FIG. 29 is the GLC profile for Example IV(D).

FIG. 30 is the GLC profile for Example IV(E).

FIG. 31 is the GLC profile for Example IV(F).

FIG. 32 is the GLC profile for Example IV(G).

FIG. 33 is the GLC profile for Example IV(H).

FIG. 34 is the GLC profile for Example IV(J).

FIG. 35 is the GLC profile for Example IV(K).

FIG. 36 is the GLC profile for Example IV(L).

FIG. 37 is the GLC profile for Example IV(M).

EXAMPLE V Preparation of Substituted Methyl Isopropyl CyclohexenoneDerivative Mixture ##STR120##

Into a 12 liter flask equipped with stirrer, thermometer, condenser,addition funnel and heating mantle is placed 250 grams of bariumhydroxide and 200 ml methyl alcohol. The resulting mixture is heated toreflux and while refluxing over a period of 20 minutes 3 kg of5-methyl-hexene-2-one mixture produced according to Example A is addedslowly to the reaction mass. The reaction mass is refluxed for a periodof 1.5 hours after which time the reaction mass is poured into 2000 mlof water. The organic phase is separated from the aqueous phase and theorganic phase is washed with water to a pH of 6-7 and distilled on an18" Goodloe column yielding the following fractions:

    ______________________________________                                               Vapor    Liquid                 Weight of                              Fraction                                                                             Temp.    Temp.    Pressure                                                                             Reflux Fraction                               Number (°C.)                                                                           (°C.)                                                                           mm/Hg. Ratio  (grams)                                ______________________________________                                         1     42/78    124/130  1.4/1.2                                                                              9.1/9.1                                                                              44.7                                    2      82      127      1.2    9.1    61.1                                    3      92      129      1.4    9.1    54.3                                    4      89      130      1.0    9.1    84.4                                    5      89      130      1.0    9.1    69.4                                    6     100      137      1.3    100%   97.5                                    7     102      138      1.2    100%   82.2                                    8     104      138      1.2    100%   98.5                                    9     105      140      1.2    100%   104.7                                  10     105      142      1.2    100%   103.0                                  11     105      142      1.2    100%   110.0                                  12     107      142      1.2    100%   80.6                                   13     105      142      1.2    100%   83.1                                   14     107      144      1.2    100%   98.9                                   15     109      145      1.2    100%   80.7                                   16     109      147      1.2    100%   75.2                                   17     109      147      1.6    100%   73.0                                   18     108      167      1.6    100%   73.9                                   ______________________________________                                    

The resulting product has an excellent peppery, guiacwood, vetiver aromawith sauge sclaree topnotes.

FIG. 38A is the GLC profile of the reaction mass prior to distillation.

FIG. 38B is the GLC profile for bulked fractions 8-15 which is thebulking responsible for the foregoing organoleptic evaluation.

EXAMPLE VI Preparation of Substituted Methyl Isopropyl CyclohexenoneDerivative Mixture ##STR121##

Into a 12 liter reaction flask equipped with thermometer, stirrer,addition funnel, reflux condenser and heating mantle is placed 250 gramsof potassium hydroxide and 200 ml methanol. The mixture is heated to 50°C. and while maintaining the temperature at 50° C. over a period of 30minutes, 3 kg of 5-methyl-hexene-2-one prepared according to Example Ais added to the reaction mixture. The reaction mixture is heated to 50°C. for a period of 1.4 hours after which time the reaction mass ispoured into 2000 ml water. The aqueous phase is separated from theorganic phase and the organic phase is washed with water to a pH of 6-7and then distilled yielding the following fractions:

    ______________________________________                                               Vapor    Liquid                 Weight of                              Fraction                                                                             Temp.    Temp.    Pressure                                                                             Reflux Fraction                               Number (°C.)                                                                           (°C.)                                                                           mm/Hg. Ratio  (grams)                                ______________________________________                                         1     52/72    120/125  0.8/0.8                                                                              9:1/9:1                                                                              55.0                                    2     72       125      0.5    9:1    75.9                                    3     72       125      0.5    9:1    78.5                                    4     72       125      0.5    9:1    89.0                                    5     73       127      0.5    9:1    58.9                                    6     86       127      0.6    100%   82.5                                    7     84       127      0.5    100%   99.6                                    8     84       127      0.5    100%   92.2                                    9     87       127      0.5    100%   79.2                                   10     85       127      0.5    100%   83.1                                   11     85       127      0.5    100%   83.4                                   12     85       127      0.5    100%   83.0                                   13     85       127      0.5    100%   89.7                                   14     85       129      0.5    100%   99.8                                   15     85       131      0.5    100%   85.4                                   16     85       135      0.5    100%   88.5                                   17     85       138      0.5    100%   91.8                                   18     85       144      0.5    100%   97.2                                   19     85       145      0.5    100%   95.7                                   20     86       152      0.5    100%   83.5                                   21     88       162      0.5    100%   67.5                                   22     91       182      0.5    100%   46.5                                   23     102      205      0.5    100%   22.7                                   24     110      210      0.5    100%   20.3                                   25     125      220      0.6    100%   21.4                                   26     132      240      0.7    100%    7.5                                   ______________________________________                                    

Fractions 7-20 of the foregoing distillation fractions are bulked andthe bulking has an interesting peppery, guiacwood, vetiver aroma withsauge sclaree topnotes and musky undertones.

FIG. 39A is the GLC profile of the reaction product prior todistillation (2 hour sample).

FIG. 39B is the GLC profile of bulked fractions 7-20 evaluated accordingto the above organoleptic evaluation.

EXAMPLE VII Preparation of Substituted Methyl Isopropyl CyclohexenoneDerivative Mixture ##STR122##

Into a 12 liter reaction flask equipped with thermometer, stirrer,addition funnel, reflux condenser and heating mantle is charged 250grams of sodium hydroxide and 2000 ml anhydrous methanol. The resultingmixture is heated and maintained at 30° C. at which time 3 kg of5-methyl-hexene-2-one prepared according to Example A is added to thereaction mass over a period of 1 hour. The reaction mass is then stirredat 30° C. until the reaction is complete as indicated by GLC. Thereaction mass is then poured into 2000 ml water. The organic phase isseparated from the aqueous phase and the organic phase is washed withwater to a pH of 6-7. The resulting material is then distilled on a 4"Splash column yielding the following fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      Pressure                                                                             Fraction                                   Number   (°C.)                                                                          (°C.)                                                                             mm/Hg. (grams)                                    ______________________________________                                         1       27/110  112/126    3.0/2.5                                                                              71.9                                        2       122     134        2.5    84.5                                        3       125     137        2.5    90.8                                        4       127     140        2.5    87.2                                        5       128     142        2.5    86.7                                        6       129     143        2.5    90.7                                        7       133     144        2.5    92.6                                        8       133     144        2.5    93.1                                        9       133     145        2.5    95.1                                       10       133     145        2.5    93.6                                       11       134     146        2.5    90.9                                       12       134     147        2.5    92.4                                       13       134     147        2.5    94.7                                       14       134     148        2.5    92.5                                       15       134     148        2.5    114.1                                      16       134     148        2.5    93.5                                       17       134     152        2.5    91.6                                       18       135     154        2.5    93.1                                       19       136     158        2.4    93.0                                       20       137     164        2.4    90.6                                       21       140     170        2.4    93.7                                       22       150     178        2.5    91.7                                       23       154     190        2.5    21.4                                       ______________________________________                                    

The resulting distillation fractions 6-16 are then bulked and evaluatedfrom an organoleptic standpoint. These fractions are evaluated as havinga peppery, guiacwood, vetiver, sandalwood aroma with sauge sclareetopnotes and musky undertones.

FIG. 40A is the GLC profile of the reaction product prior todistillation.

FIG. 40B is the GLC profile of bulked fractions 6-16 of the foregoingdistillation.

EXAMPLE VIII Perfume Formulation

The following sandal cologne perfume formulation is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                             Bergamot oil              200                                                 Orange oil                150                                                 Lemon oil                 100                                                 Mandarin oil              50                                                  Eugenol                   10                                                  4-(4-methyl-4-hydroxy amyl)                                                                             30                                                  delta.sup.3 -cyclohexane                                                      carboxaldehyde                                                                3-methyl-4(2,6,6-trimethyl-                                                                             5                                                   2-cyclohexene-1-yl)-3-                                                        buten-2-one                                                                   methyl-N3,7-dimethyl-     5                                                   7-hydroxy-octylidene                                                          anthranilate                                                                   ##STR123##                 5                                                 2-methyl-5(2-exo-methyl-3-                                                                              100                                                 methylene-bicyclo-[2.2.1]-hept-                                               2-yl)3-penten-2-ol)                                                           (prepared according to U.S.                                                   Pat. No. 4,000,050)                                                           Mixture of substituted methyl                                                                           40                                                  isopropyl cyclohexenones prepared                                             according to Example I, bulked                                                fractions 7-22                                                           ______________________________________                                    

The mixture of substituted methyl isopropyl cyclohexenones preparedaccording to Example I imparts to this sandal cologne formulation awarm, intense, peppery, guiacwood-like, vetiver, sandal odor with saugesclaree topnotes and musky undertones.

EXAMPLE IX Lilac Perfume

The following mixture is prepared:

    ______________________________________                                                                Parts                                                                         by                                                    Ingredients             Weight                                                ______________________________________                                              Terpineol                 448                                                 Hydroxy citronellal       133                                                 Heliotropin               160                                                 Phenylethyl alcohol       50                                                  Benzyl acetate            82                                                  Anisaldehyde              95                                                  Oil of cananga            6                                                   Coumarin                  3                                                   Alpha ionone              6                                                   Methyl jasmonate          8                                                   2,3-dimethyl-hydroquinone 6                                                   p-methoxy acetophenone    3                                                   Mixture of substituted isopropyl                                                                        35                                                  methyl cyclohexenones prepared                                                according to Example III, bulked                                              fractions 4-18                                                          ______________________________________                                    

The addition of the substituted methyl isopropyl cyclohexenones producedaccording to Example III to this lilac formulation impart to itcompatible fresh, floral, citrusy, and spicy aroma nuances which renderit more aesthetically pleasing than the ordinary lilac formula andrender it more "natural-like".

EXAMPLE X Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of the perfume substance set forth inTable II below. The resulting substance has an excellent aroma as setforth the Table II below:

                  TABLE II                                                        ______________________________________                                        Substance          Aroma                                                      ______________________________________                                        Mixture of substituted methyl                                                                    A peppery, guiacwood,                                      isopropyl cyclohexenones                                                                         vetiver, sandalwood, fruity,                               prepared according to Example I,                                                                 aroma with sauge sclaree                                   bulked fractions 7-22                                                                            topnotes and musky                                                            undertones                                                 Product prepared according to                                                                    A peppery, guiacwood,                                      Example II, bulked fractions                                                                     vetiver aroma with sauge                                   2-6                sclaree topnotes                                           Product prepared according to                                                                    A fresh, floral, citrusy,                                  Example III, bulked fractions                                                                    spicy aroma                                                4-18                                                                          Perfume composition of                                                                           A sandalwood aroma with                                    Example VIII       peppery, guiacwood, vetiver,                                                  musky and sauge sclaree                                                       nuances                                                    Perfume composition of                                                                           A lilac aroma with fresh,                                  Example IX         floral, citrusy and spicy                                                     nuances                                                    ______________________________________                                    

EXAMPLE XI Perfumed Liquid Detergent

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApril 6, 1976, the specification for which is incorporated by referenceherein) with aroma nuances as set forth in Table II of Example X supraare prepared containing 0.10%, 0.15% and 0.20% of the perfume substancesas set forth in Table II of Example X. They are prepared by adding andhomogeneously admixing the appropriate quantity of fragrance formulationas set forth in Table II of Example X in the liquid detergents. Thedetergents all possess excellent aromas as set forth in Table II ofExample X, the intensities increasing with greater concentrations ofperfume substance of Table II of Example X.

EXAMPLE XII Preparation of Colognes and Handkerchief Perfumes

Perfumery substances as set forth in Table II of Example X areincorporated into colognes in concentrations of 2.0%, 2.5%, 3.0%, 3.5%,4.0%, 4.5% and 5.0% in 75%, 80%, 85%, 90%, and 95% aqueous food gradeethanol; and into handkerchief perfumes at concentrations of 15%, 20%,25% and 30% (in 80%, 85% and 95% aqueous food grade ethanol).Distinctive and definitive aromas as set forth in Table II of Example Xare imparted to the cologne and to the handkerchief perfume at all thelevels indicated above.

EXAMPLE XIII Preparation of Soap Compositions

100 grams of soap chips (IVORY® produced by the Procter & GambleCompany, Cincinnati, Ohio) are mixed with one gram of each of thesubstances as set forth in Table II of Example X supra, untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of 8 hours. The resulting liquids are placed into soapmolds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table II of Example X.

EXAMPLE XIV Preparation of Solid Detergent Compositions

Detergents are prepared from the following ingredients according toExample I of Canadian Pat. No. 1,007,948, the specification for which isincorporated by reference herein:

    ______________________________________                                                                Parts                                                                         by                                                    Ingredients             Weight                                                ______________________________________                                              Neodol ® 45-11 (a C.sub.14-15                                                                       12                                                  alcohol ethoxylated                                                           with 11 moles of ethylene                                                     oxide                                                                         Sodium carbonate          55                                                  Sodium citrate            20                                                  Sodium sulfate, water brighteners                                                                       q.s.                                          ______________________________________                                    

This detergent is a "phosphate-free" detergent. A total of 100 grams ofthis detergent per sample is admixed with 0.15 grams of each of theperfume substances of Table II of Example X. Each of the detergentsamples has excellent aromas as set forth in Table II of Example X.

EXAMPLE XV

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the specification for which is incorporated by referenceherein), a non-woven cloth substrate useful as a drier-added fabricsoftening article of manufacture is prepared wherein the substrate, thesubstrate coating and the outer coating and the perfuming material areas follows:

1. a water dissolvable paper as the substrate ("Dissolvo Paper")

2. Adogen 448 (melting point 140° F.) as the substrate coating and

3. an outer coating having the following formulation (melting pointabout 150° F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the per fumery substances as set forth in Table II ofExample X

A fabric softening composition prepared as set forth above having aromacharacteristics as set forth in Table II of Example X consists of asubstrate having a weight of about 3 grams per 100 square inches, asubstrate coating weighing about 1.85 grams per 100 square inches ofsubstrate and an outer coating weighing about 1.4 grams per 100 squareinches of substrate is created, thereby providing a total aromatizedsubstrate and outer coating weight ratio of about 1:1 by weight of thesubstrate. The aromas as set forth in Table II of Example X is impartedin pleasant manners to head spaces in the driers on operation thereofusing the drier-added fabric softening non-woven fabric articles.

EXAMPLE XVI

A tobacco blend is made up by mixing the following materials:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           ______________________________________                                    

The above tobacco is used in producing cigarettes and the followingformulation is compounded and incorporated into each of thesecigarettes:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Ethyl butyrate 0.05                                                           Ethyl valerate 0.05                                                           Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above flavor is incorporated into model "filter" cigarettes at therate of 0.1%. One-third of these model cigarettes are treated in thetobacco section with the substituted methyl isopropyl cyclohexenonemixture produced according to Example I, bulked fractions 11-19 at 400ppm per cigarette. Another one-third of these model cigarettes aretreated in the filter with bulked fractions 11-19 of the methylisopropyl cyclohexeneone mixtures produced according to Example I at therate of 2×10⁻⁴ grams. When evaluated by paired comparison, thecigarettes treated both in the tobacco and in the filter with thesubstituted methyl isopropyl cyclohexenone derivatives preparedaccording to Example I are found, in smoke flavor, to be moretobacco-like with enhanced sweet, citrusy characteristics.

Prior to smoking, the tobacco composition has a woody, peppery, citrusyaroma profile. The sweet, citrusy character in the smoke flavor isimparted both in the main stream and in the side stream on smoking.

What is claimed is:
 1. At least one compound defined according to thestructure: ##STR124## wherein one of the dashed lines represents acarbon-carbon double bond and the other of the dashed lines represents acarbon-carbon single bond; wherein R₄ represents methyl or ethyl;wherein one of R₁, R₂ and R₃ represents 2-methyl-1-propenyl or2-methyl-1-propylidenyl; and the other of R₁, R₂ and R₃ representhydrogen; with the provisos that:(i) when the dashed line at the 3-4position is a double bond, then R₃ is hydrogen or 2-methyl-1-propenyl;(ii) when the dashed line at the 2-3 position is a double bond, then R₂is hydrogen or 2-methyl-1-propenyl; (iii) when R₄ is ethyl, then R₂ ismethyl and the double bond is at the 2-3 position; and (iv) when R₄ ismethyl, then R₂ is hydrogen; 2-methyl-1-propenyl or2-methyl-1-propylidenyl.
 2. The compound of claim 1 having a structureselected from the group consisting of: ##STR125##
 3. The compound ofclaim 1 wherein the compound has a structure selected from the groupconsisting of: ##STR126##
 4. A process for carrying out the reaction:##STR127## wherein R₄ " is hydrogen or methyl; wherein R₄ ' is methyl orhydrogen; wherein R₁, R₂, R₃ and R₄ are defined according to claim 1;and wherein the reaction is carried out in the presence of a catalystselected from the group consisting of sodium hydroxide, potassiumhydroxide and barium hydroxide and in the presence of a solvent selectedfrom the group consisting of ethanol, methanol and isopropanol; and at atemperature in the range of from about 25° C. up to about 120° C.;wherein one of the dashed lines represents a carbon-carbon single bondand the other of the dashed lines represents a carbon-carbon doublebond.
 5. The product prepared according to the process of claim
 4. 6.The process of claim 4 wherein R₄ " and R₄ ' represent hydrogen and R₄is methyl.
 7. The product produced according to the process of claim 6.